Electrodialysis demineralization



May 17, 1960 N. W. ROSENBERG ELECTRODIALYSIS DEMINERALIZATION Filed Aug. 1:5. 1957 nited States Patent "O 4 This invention relates to thecontinuous removaliof electrolytes from solutions and more specifically to the 1952, lby; Katz et al., discloses for continuously "and simultaneously concentratingar'id diluting twovsolutions ofv electrolyteswhereby'gafplurality ofdiluting and/concentrating chambers is employed Ice 2,937,126

.Patented Mey 17 1969 I a method and lapparatus and'apart ofthe ellluent from one set of chambers (concentratingor diluting)iis.passedV through another setof chambers connected in series to further concentrateor dilute the solution.' -In this method the' eluent stream fromthe chambers-isnot recirculated throughthe same chambersIrv but is Vrather passed through anotherfsetof :chambers vfor further ftransfer of electrolyte.V .11n gvthis apparatus, a Yseparatesystemof feedfand discharge'fr simultaneous concentration and dilution of 'two solutions in an electrodialysis cell. More particularly this invention comprises an improvement overY known methods/,and apparatus for deminera'livzing solutions whereby the ejluent stream from the concentrating chambersof an, electrodialysis cell is circulated to the electrode compartments f stream is thus eliminated. v i n Electrodialysis apparatus `for the continuous demineralization of solutions have been disclosed.in-,patentapplications Ser. No. 300,302, filed July 22, 1,952, now-,Patent No. 2,860,095, and Ser.No. 428072 filed, May 6, 1954, now Patent No.2,848,403. v ,sllchapparatus utilizes an electrodialysis cell in which a, direct.. electric-.current is used to continuouslyrtransfer ionshfrorm an inuent s oand a separate pump for the electrode compartment feed lution through ionselectiv'e permeable membranes into an adjoining chamber of the cell. i By such a process the solution inone of said chambers is'continuously diluted while the solution in the adjoining chamber is continuously concentrated. The chambers are separated ,by

ionselective permeable membranes which permit transf fer of ions of one electric chargeV Yand bar the transfer of ions'of the oppositecharge. The demineralizing electrodialysis cell consists of a plurality of diluting charnbers, in which one solution is diluted, alternately disposed between a plurality of concentrating chambersin which a second solution is concentrated, the separating permselective membranes, and the electrodes for Ythe passage of direct current through the cell. .Such`ele`ctr'odialysisf'apparatus for demineralizing or: deionizing solutions may consist of any number of concentrating and. diluting 1 chambers, for example 100 of each, and two electrode chambers containing anodeand cathode. In modifying the concentrations of solutionsin vsuch an apparatus described above,.y it is rwell knownto employ three feed systems for the circulation ofiliquids in the cell. For example, onefpumpY and y'piping'system feeds the diluting chambers and carries` away the diluted solution for recirculation or exhaust. Y- Similarly, a'second pump and piping system yfeeds the concentrating chamber and carries away the concentratedY solution for recirculation or exhaust. The third pump and piping sys# tem passes a feed stream throughtheanode' and cathode chambers thereby continuously,A removing the products formed at the electrodes.

In patent application Sen-No. 428,072," filed May 6,

1954, it is disclosed that the streams from the three systems above can be recirculated in whole or in part to maintain' equal pressure drops across the aforementioned membranes. In addition,the stream from the'concentrating chambei can be recirculated in'order to increase the concentration and reduce the fluid consumption of the cell. i

I'atent application ASer. No. 300,302, ytiled July .22,l y

paratusdescribed'above, whether streams lare recir'cu-A flated throughlthefsa'me chambers or'a different-set of .chambers connected Vinseries, that a separatev pump and piping/system for. the ,electrode feed streamhasbeen' em'- vployed In application SerJNo'.A 428,072 ledMay 6, 1954,

vit is Ldisclosedthatfthev electrode lfeed maybe continuously recirculated Yand :thatr theipH of the cathode Afeed must be acid to prevent ynletal'salt precipitation in the cathode chamber. l v f I' V The'maintenance of a separate pump and pipingsystemffor the v'electrode-feed' has several disadvantages which are eliminatedby'the presentvinvention. lIfthi: feed stream to the electrodes is dischargedwithouterecirculation, Ythe waterfconsumption is prohibitive. Consequently it was common to recirculate the electrode `feed `stream continuously through anl electrode feed pumping system. Recirculation of the liquid fromY the 'electrode compartments'iuvolves several difficulties which are'exl pensive to overcome. -For'example in n apparatus'for the demineralzing of v`sea Water, chlorine'land'oxyge'n gasesare VVformed at"the-anode=ai1d pickedtipby"the anode feed stream. A gas trap was required to lr'e'rn'ove -these corrosiveA- gases :before 'the anode feed could kbe .recirculated Alsor=as:mentioned,fthe additionvof acid is necessary to maintain anfacid pH in the cathode cham'- ber; they acid further increasedthe corrosiveness'of'the electrode feed water. Inaddition to corrosion of pipes and pump, it was found thtthe gases in the feedfwater tended to cause the electrode feedpump to becomefgasbound'. The present invention envisions an improvement `over the electrode feedlsy'stem'describedabove by eliminating.; the electrode feed pump and separate circulating system and by circulating-a portion of theconcentrate feed stream into the ,electrode` compartments, adjusting thel pH as necessary, and byV discarding the electrode chamber discharge containing dissolved gases. flf `'The advantages' vof Jsuch a method and apparatus Yfor the electrode feed stream over. vthe use of av Aseparateelec:- t'rodeteed vsystem' 'in' an electrodialysis-cell are readily apparent.v The initial `capital investment in a deionizing unit is -reduced by eliminating a pump. 'lfheunit is more reliable because there Jis no electrode feed-system .in which breakdowns or gasleaks can occur. Y,Maintenance costs` are therebyreduced. YVIn addition vthe necessity `V,of pumping,A handling, and removing gases from the stream is obviated@` ,A ,7'

The object ofk this invention is to continuously remove the electrolytes `from a solution in an electrodialysis more economically and eciently than is possiblev by existing apparatus. L l. i

Itis also an object of the invention tol reduce-:maui tenance and breakdowns in the pumping systemsby eliminating the electrode feed pump. 1 j This invention will be morefully understoodlfv-from the following detailed descriptionof representative bodiments of the invention wherein reference is made to the drawing in which:

Figure 1 is a schematic representation of an electrodialysisgcell in which a portion of the concentrate efluent is passed through the electrode chambers.

Figure 2 is a schematic representation of an electrodialysis cell which includes' the system for recirculating the concentrate effluent while at the same time passing a portion `of the concentrate eluent lthrough the electrode chambers.

In the electrodialysis cellin Figure l diluting chambers 1 (D) are -alternately disposed with concentrating chambers 2 (C). It is understood 4that a plurality of diluting and concentrating chambers may `be used, for example 100 of each. The anode chamber 3 and `the Acathode' chamber 4 contain the electrodes 20 .and 21,

respectively, for the passage of the direct current through Y the cell. Y

Separating the chambers are ion-selective permeable membranes, membranes selectively permeable to anion A and membranes selectively permeable to cations K. Permselective membranes of the type used in this apparatus may be preparedby methodsdisclosed in U.S. Patent No. 2,636,851 and U.S. Patent No. 2,730,768.v

The solution to bediluted is introduced into the dilut- -ing chambers by the iniluent manifold 5 of the diluting circulatory system. The eiluent solution fom the .diluting chamber is withdrawn through manifold 6 to be passed through successive cells or removed from the unit, depending on the degree of dilution desired. The concentrating chambers are fed through influent manifold 7 while the concentrate effluent stream is drawn Aoff through eiiiuent manifold 8.

The anode feed stream 9 is taken off the concentrate efuent line` 8 thereby eliminating a separate electrode pump. The anode efduent 10 is discarded `because it contains free chlorine and oxygen gases formed at the electrode- The presence of these corrosive gases makes `it undesirable to recirculate the discharge from the anode chamber.

The feed stream 11 for the cathode chamber is likewise taken from the concentrate eflluent line 8, and acid is added by a line 12 from an acid proportionating pump The remaining portion of the con- However in the cell illustrated schematically in Figure 2,

the anode feed line 9 and the cathode feed line 11 are taken directly olf of a concentrate recirculation ypump 15. The concentrate eluent 8 is-recir'culated through Conduit 16 through the circulating pump 15, Waste being removed at 17 and raw feed water added continuously at 18. The eluent from the cathode chamber may be discarded at 13 as shown in Figure 1, or saideluent may be reinjected at 19 into rthe concentrate effluent stream to be recirculated. n

The demineralization of naturally occurring brackish water will serve as an illustration of the operation'of the apparatus described above, but it must be understood that the method Aand apparatus for electrode feed is not limited to brackish water but is applicable to any simultaneous concentration and dilution of solutions in an electrodialysis cell.

The brackish water to be demineraliz'ed is fed into the diluting chambers of the electrodialysis `unit while the concentrate feed stream is pumped into the concentrating cells. Upon passing a direct current through the electrodes the ions from the brackish water areV transferred through `the .permselective membranes into the adjoining concentrating chambers. The eluent stream from the concentrating chambers can be recirculated by means of a concentrate circulation pump, as shown in Figure 2, to economize on water consumption. A certain amount of the concentrate stream is continuously drawn off and discarded while raw feed water is continuously added to maintain constant flow. The amount of concentrate waste depends upon the initial salt concentration in the raw feed water. Where initial salt concentration, for example of CaSO4, is high,4a slight salt addition in the concentrating chambers Willcause precipitation of the salt in the chambers or the lines and the amount of concentrate waste will be high. Depending on initial salinity of the feed water,` concentrate waste may be 10% or greater of the total flow through the unit, or as low as 2%.

The principal embodiments of this invention are method and apparatus for utilization of a portion of the concentrate efliuent stream for electrode feed. The anode chamber may be fed directly from the concentrate feed manifold if the concentrate eiluent is recirculated or it may be fed off Vthe concentrate euent line if the concentrate effluent line is not recirculated. The etlluent from the anode chamber contains chlorine and oxygen gases which would have great corrosive effect on pumps and piping if recirculated. Hence, the anode eftluent is discarded as waste, comprising about 1% of the total liquid flow through the unit. lThe anode waste may be considered to be a Vportion of the concentrate wase mentioned above since it is removed from the concentrate circulating system.

The cathode chamber is lfed from a line olf the concentrate circulating pump or from the concentrate eiuent stream to which feed line is connected a lineV from an acid proportionating pump. As pointedout, pH adjustment of the cathode feed is necessary to prevent precipitation of salts, for Vexample CaSO4, in the cathode chamber. If pH adjustment is necessary to prevent precipitation in the concentrating chambers, the concentrate feed stream will be sufficiently acid to prevent precipitation in lthe'cathode chamber. The acidic efiiuent from the cathode chamber contains hydrogen gas formed lat the cathode. The eluent is discarded because the gas in the liquid tends to bind the circulating pump, and the dissolved hydrogen may be dangerous as explosive if discharged with the concentrate waste. Anode and cathode eluents are combined and discarded separately because of their dissolved gases. The cathode etiluent would also be discarded if acid adjustment of the concentrate feed is not desired. As in the case of the anode eluent, the volume of discharge from the cathode chamber is about 1% of the total ow in the unit and can be considered part of the concentrate waste. The cathode effluent can, however, exit into' the concentrate recirculation system where acid adjustment of concentrate feed is desired.

It is also understood that the effluent from the concentrate chambers does not have to be recirculated but can be directly discharged if desired. In that case a portion of the concentrate effluent would be fed to the electrode chambers directly.

The following example will serve to illustrate the principles and use of this invention more fully but the invention is not limited thereto.

Example 1 A membrane demineralizer containing 1,50 diluting chambers 1 and l5() concentrating chambers 2 separated by selective membranes, and two electrode chambers and 4 as shown in Figure 2 was used to treat a natural brackish water containing 1500 ppm. of NaHCO3 and 500 p.p.rn. of MgCl2, and traces of other salts.

The brackish water was fed into the diluting chambers through a dilute feed system at 11200 gallons per hour. Brackish Water was also fed into concentrating chambers and the electrode chambers through the concentrate circulation system. The eiluent from the concentrating was discarded by conduit 17 in Figure 2.

chambers was recirculated through the concentrate circulation pump 1S. In continuous operation the concentrate circulation pump circulated the concentrate and electrode feed at a rate of 1200 gallons per hour at 20 p.s.i. Of this ow, 30 gallons per hour is fed to the cathode chamber, being mixed with 0.1 gallon per hour of 20% H2SO4; and 30 gallons per hour was fed to the anode chamber.

The efluent from the cathode chamber was reinjected into the circulating concentrate elfluent stream where it served to maintain the pH at a value of 6.5. The anode effluent, at a rate of 30 gallons per hour, Was discarded because of the corrosiveness of the dissolved chlorine and oxygen gases. In addition to the discharge of the anode efliuent, 90 gallons per hour of concentrate eflluent To make up for the total 120 gallons per hour discharge, 120 gallons per hour of raw feed water was added through conduit 18. In continuous operation, the total of 120 gallons per hour discharged from the concentrate circulation system (30 g.p.h. from the anode and 90 g.p.h. from the concentrate eiiiuent) contained the entire amount of salt transferred from the diluting compartments plus the salt injected in the raw feed water. The natural brackish water was reduced in total salts from 2000 parts per million of NaHCO3 and MgCl2 to 500 parts per million at a rate of 1200 gallons per hour. The waste discharged from the concentrate effluent contained a total solids level of 17,000 parts per million. A direct current of 25 amperes at a voltage of 350 volts was used in operating the demineralizing unit.

Having thus disclosed my invention and described in detail representative and preferred embodiments thereof, I claim and desire to secure by Letters Patent:

1. The method of modifying the concentration of an electrolyte solution comprising passing a first feed stream from a common manifold through the diluting chambers of an electrodialysis unit having a plurality of diluting and concentrating chambers dened between ion-selective membranes and two end electrode chambers likewise separated from their adjacent chambers by ion-selective membranes, passing a second feed stream in parallel concurrent flow from a separate common manifold through the concentrating chambers, passing electrolytes through both electrode chambers, at least one of which electrolytes is a portion of the efuent from the concentrating chambers, recirculating at least a portion of the remaining eluent from the concentrate chambers back to the inuent of the concentrate chambers, and passing a direct electric current through said chambers and membranes.

2. The method of claim 1 wherein a portion of the eiuent from the concentrating chambers is passed through the anode chamber.

3. The method of claim 1-wherein a portion of the euent from the concentrating chamber is acidied and then passed through the cathode chamber.

4. The method of claim 1 wherein a portion of the i trolyte solutions in an electrodialysis unit comprising a plurality of concentrating and diluting chambers between two end electrode chambers, said chambers being separated oy ion-selective membranes, means for continuously passing a feed stream from a common manifold through the diluting chambers, means for passing a second feed stream in parallel concurrent flow from a separate common manifold through the concentrating chambers, means for passing a portion of the effluent from the concentrating chambers through at least one electrode chamber, means for recirculating a portion of the remaining effluent from the concentrating chambers to the influent of said concentrating chambers, and means for passing a direct electric current transversely through all said chambers and membranes.

7. Apparatus for modifying the concentration of electrolyte solutions in an electrodialysis unit comprising a plurality of concentrating and diluting chambers between two end electrode chambers, said chambers being separated by ion-selective membranes, means for continuously passing a feed stream from a common manifold through the diluting chambers, means for passing a second feed stream in parallel concurrent flow from a separate common manifold through the concentrating chambers, means for acidifying a portion of the effluent from the concentrating chambers and passing the same into the influent of the cathode electrode chamber, means for recirculating a portion of the remaining ellluent from the concentrating chambers to the influent of said concentrating chambers, and means for passing a direct electric current transverse- 1y through all said chambers and membranes.

References Cited in the le of this patent UNITED STATES PATENTS 2,796,395 Roberts June 1s, 1957 2,863,813 Juda et a1 Dec. 9, 1958 FOREIGN PATENTS 682,703 Great Britain Nov. 12, 1952 750,500 Great Britain June 20, 1956 504,756 Belgium Aug. 8, 1951 OTHER REFERENCES Langelier: Journal American, Water Worksr Assoc., September 1952, pp. 845-848.

Arnold et al.: The Industrial Chemist, July 1953, pp. 295-298.

Walters et al.: Industrial and Engineering Chemistry, vol. 47, No. 1, January 1955, pp. 61-66. 

1. THE METHOD OF MODIFYING THE CONCENTRATION OF AN ELECTROLYTE SOLUTION COMPRISING PASSING A FIRST FEED STREAM FROM A COMMON MANIFOLD THROUGH THE DILUTING CHAMBERS OF AN ELECTRODIALYSIS UNIT HAVING A PLURALITY OF DILUTING AND CONCENTRATING CHAMBERS DEFINED BETWEEN ION-SELECTIVE MEMBRANES AND TWO END ELECTRODE CHAMBERS LIKEWISE SEPARATED FROM THEIR ADJACENT CHAMBERS BY ION-SELECTIVE MEMBRANES, PASSING A SECOND FEED STREAM IN PARALLEL CONCURRENT FLOW FROM A SEPARATE COMMON MANIFOLD THROUGH THE CONCENTRATING CHAMBERS, PASSING ELECTROLYTES THROUGH BOTH ELECTRODE CHAMBERS, AT LEAST ONE OF WHICH ELECTROYLTES IS A PORTION OF THE EFFLUENT FROM THE CONCENTRATING CHAMBERS, RECIRCULATING A LEAST A PORTION OF THE REMAINING EFFLUENT FROM THE CONCENTRATE CHAMBERS BACK TO THE INFLUENT OF THE CONCENTRATE CHAMBERS, AND PASSING A DIRECT ELECTRIC CURRENT THROUGH SAID CHAMBERS AND MEMBRANES. 